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In the title compound, [VO(C16H16N2O2)(H2O)]NO3·0.76H2O, the V atom has a distorted octahedral coordination geometry with a long V—O(water) bond, 2.225 (1) Å, trans to V=O, 1.594 (1) Å. The V atom is 0.260 Å out of the plane defined by the N and O atoms of the bis­(salicyl­idene)­ethyl­enediaminate ligand and is displaced towards the vanadyl O atom. The coordinated water mol­ecule is hydrogen bonded to one O atom of the nitrate ion so that pairs of cations are linked by two O—H...O...H—O bridges to give neutral centrosymmetric dimers. This is a different bridging arrangement from that found in either of the polymorphs of the an­hydro­us compound. There is also a weak hydrogen bond between a nitrate O and the partially occupied water of crystallization.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801009850/na6088sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801009850/na6088Isup2.hkl
Contains datablock I

CCDC reference: 170745

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.003 Å
  • H-atom completeness 99%
  • Disorder in solvent or counterion
  • R factor = 0.036
  • wR factor = 0.040
  • Data-to-parameter ratio = 15.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 29.68 From the CIF: _reflns_number_total 4646 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 5089 Completeness (_total/calc) 91.29% Alert C: < 95% complete PLAT_302 Alert C Anion/Solvent Disorder ....................... 13.00 Perc. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C16 H17.52 N3 O7.76 V1 Atom count from the _atom_site data: C16 H17.18 N3 O7.76 V1 CELLZ_01 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C16 H17.52 N3 O7.76 V1 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 32.00 32.00 0.00 H 35.04 34.36 0.68 N 6.00 6.00 0.00 O 15.52 15.52 0.00 V 2.00 2.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

Complexes of the type VVO(Schiff base)Y (Y = Cl, ClO4, NO3) can be prepared by oxidizing VIVO(Schiff base) with (NH4)2Ce(NO3)6 in acetonitrile followed by the addition of HY (Nakajima et al., 1990). [VVO(salen)(H2O)](NO3) (salen is N,N'-ethylene-bis(salicylideneaminato) prepared in this way was found to crystallize as a mixture of two polymorphs, a monoclinic, (1), and a triclinic form, (2) (Hazell et al., 2001). An IR spectrum of the bulk product showed two VO stretching frequencies, 965 and 972 cm-1, corresponding to the two slightly different VO distances in the two polymorphs. A slightly modified synthesis yielded a product that gave a single sharp VO absorption, 974 cm-1, but with cell dimensions differing from those of either of the two polymorphs. A structure determination showed the new compound to contain an extra water of crystallization.

The title compound, (I), contains [VVO(salen)(H2O)]+ and NO3- ions, the cations are linked by hydrogen bonds via the nitrates to give neutral centrosymmetric dimers (see below and Fig. 1). The V atom is coordinated to two N and two O atoms of salen, to the vanadyl oxygen and to a water molecule which is trans to the vanadyl O atom, this octahedral arrangement is distorted so that the V atom is displaced out of the N2O2 plane in the direction of the vanadyl O atom. The displacement, 0.260 Å, is similar to that in (1), 0.255 Å, and (2), 0.260 Å, and is is slightly smaller than the value of 0.270 Å observed in the cation of [VVO(salen)(H2O)]2(Cu2Cl4), (3) (Banci et al., 1984). The VO distances in compounds (1), (2) and (3) and the title compound (I) are 1.597 (1), 1.588 (3), 1.590 (5) and 1.594 (1) Å, respectively. The V—O(water) distances are 2.257 (1), 2.230 (3), 2.310 (5) and 2.225 (1) Å, respectively, in the four compounds, which are much longer than the usual VV—O distance, cf. V—O(salen) distances of 1.805–1.838 Å. The coordinated water molecules are hydrogen bonded to the nitrate ion so that there are two nitrate bridges between pairs of cations with O(nitrate)···O(water) = 2.720 (2) and 2.742 (2) Å and there is a weaker hydrogen bond, O(nitrate)···O(water) = 2.909 (4) Å to the water of crystallization. In (1) and (2), the cations are also linked by hydrogen bonds via the nitrates, a major difference is that here only one nitrate O atom is involved in the bridging, i.e. H···O(NO2)···H instead of H···O(NO)O···H. The V···V distance is 8.409 (1) Å which is longer than those of 7.846 (1) Å in (1) and 7.850 (2) Å in (2). There are three different N—O bond distances, 1.265 (2) Å to the O atom involved in the strongest hydrogen bond, 1.226 (2) Å to the O atom not hydrogen bonded and 1.241 (2) Å to the O which is only weakly hydrogen bonded. The water of crystallization is disordered over two sites with occupations of 0.59 (1) for O8 and 0.17 (1) for O(9). The dimers pack so that the salen groups are parallel to each other as in (1), the density is 1.582 Mg m-3which is the same as that for the triclinic polymorph (1).

Experimental top

4.904 g (8.945 mmol) of (NH4)2Ce(NO3)6 in 450 ml acetonitrile was added to 2.500 g (7.502 mmol) of VIVO(salen) in 375 ml acetonitrile. The volume was reduced to 250 ml by boiling on a water bath and 225 ml of 1.5 M nitric acid was added. After 24 h, 0.866 g (2.03 mmol) of dark-violet crystals were collected by filtration. A furthur 1.970 g (4.613 mmol) of smaller crystals precipitared during the next week. IR spectra (KBr disc, Perkin Elmer FT–IR spectrometer) ν(VO) 974 cm-1 for both crops of crystals. This preparation differs from that described in Hazell et al. (2001), in that here the nitric acid was added directly to the solution of VIVO(salen) instead of to the solid.

Refinement top

The H atoms of the ligand were constrained to have C—H = 0.95 Å and Uiso = 1.2Ueq for the atom to which they are attached. The H atoms of the water molecules O4 and O8 were obtained from a a difference map and kept fixed, It was only after O9 (which is only 1 Å from O8) was included in the refinement that the H atoms on O8 could be located. Those of O9 were neither located or included in the refinement.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1997 ) and KRYSTAL; program(s) used to refine structure: modified ORFLS (Busing et al., 1962) and KRYSTAL (Hazell, 1995); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL; software used to prepare material for publication: KRYSTAL.

Figures top
[Figure 1] Fig. 1. View of the title compound showing the labelling of the non-H atoms. Displacement ellipsoids are shown at 50% probability levels and the H atoms of the water molecules are shown as small circles of arbitrary radius. [Symmetry code: (i) 1 - x, 1 - y, 2 - z.]
N,N'-ethylene-bis(salicylideneaminato-N,O oxovanadium(V) nitrate hydrate(0.76) top
Crystal data top
[VO(C16H16N2O2)(H2O)]NO3·0.76H2OZ = 2
Mr = 426.97F(000) = 439.20
Triclinic, P1Dx = 1.582 Mg m3
Hall symbol: -p 1Mo Kα radiation, λ = 0.71073 Å
a = 9.482 (1) ÅCell parameters from 9019 reflections
b = 9.859 (1) Åθ = 2.1–29.7°
c = 10.324 (2) ŵ = 0.60 mm1
α = 74.995 (2)°T = 120 K
β = 74.022 (2)°Block, violet
γ = 85.559 (3)°0.50 × 0.40 × 0.24 mm
V = 896.1 (2) Å3
Data collection top
Siemens SMART CCD
diffractometer
4646 independent reflections
Radiation source: x-ray tube4190 reflections with I > 3σ(I)
Graphite monochromatorRint = 0.074
ω rotation scans with narrow framesθmax = 29.7°, θmin = 2.1°
Absorption correction: integration
(XPREP; Siemens, 1995)
h = 1312
Tmin = 0.741, Tmax = 0.872k = 1313
12081 measured reflectionsl = 1413
Refinement top
Refinement on F0 restraints
Least-squares matrix: full2 constraints
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.040 w = 1/{[σcs(F2) + 0.2 + 1.03F2]1/2 - |F|}2
S = 0.97(Δ/σ)max = 0.002
4190 reflectionsΔρmax = 0.40 (8) e Å3
264 parametersΔρmin = 0.81 (8) e Å3
Crystal data top
[VO(C16H16N2O2)(H2O)]NO3·0.76H2Oγ = 85.559 (3)°
Mr = 426.97V = 896.1 (2) Å3
Triclinic, P1Z = 2
a = 9.482 (1) ÅMo Kα radiation
b = 9.859 (1) ŵ = 0.60 mm1
c = 10.324 (2) ÅT = 120 K
α = 74.995 (2)°0.50 × 0.40 × 0.24 mm
β = 74.022 (2)°
Data collection top
Siemens SMART CCD
diffractometer
4646 independent reflections
Absorption correction: integration
(XPREP; Siemens, 1995)
4190 reflections with I > 3σ(I)
Tmin = 0.741, Tmax = 0.872Rint = 0.074
12081 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.040H atoms treated by a mixture of independent and constrained refinement
S = 0.97Δρmax = 0.40 (8) e Å3
4190 reflectionsΔρmin = 0.81 (8) e Å3
264 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
V0.84705 (3)0.28602 (3)0.78131 (3)0.0154 (2)
O10.9750 (1)0.4121 (1)0.7857 (1)0.020 (1)
O20.7995 (1)0.1624 (1)0.9528 (1)0.019 (1)
O30.9570 (1)0.1899 (1)0.6956 (1)0.022 (1)
O40.6768 (1)0.4136 (1)0.8940 (1)0.024 (1)
N10.8049 (2)0.4396 (2)0.6141 (1)0.019 (1)
N20.6686 (2)0.2064 (2)0.7458 (1)0.021 (1)
C10.9768 (2)0.5528 (2)0.7578 (2)0.019 (1)
C21.0569 (2)0.6160 (2)0.8212 (2)0.024 (1)
C31.0648 (2)0.7615 (2)0.7877 (2)0.031 (1)
C40.9963 (3)0.8441 (2)0.6918 (2)0.032 (1)
C50.9186 (2)0.7820 (2)0.6277 (2)0.027 (1)
C60.9075 (2)0.6345 (2)0.6598 (2)0.021 (1)
C70.8317 (2)0.5718 (2)0.5866 (2)0.021 (1)
C80.7209 (2)0.3880 (2)0.5359 (2)0.025 (1)
C90.5988 (2)0.2991 (2)0.6454 (2)0.027 (1)
C100.6270 (2)0.0781 (2)0.8002 (2)0.024 (1)
C110.6830 (2)0.0186 (2)0.9051 (2)0.021 (1)
C120.6453 (2)0.1616 (2)0.9402 (2)0.027 (1)
C130.6906 (2)0.2565 (2)1.0440 (2)0.029 (1)
C140.7698 (2)0.2101 (2)1.1193 (2)0.028 (1)
C150.8066 (2)0.0699 (2)1.0895 (2)0.024 (1)
C160.7658 (2)0.0259 (2)0.9807 (2)0.019 (1)
N30.5320 (2)0.3012 (2)1.2758 (2)0.025 (1)
O50.5377 (2)0.3968 (1)1.1658 (1)0.033 (1)
O60.5796 (2)0.1825 (2)1.2654 (2)0.046 (1)
O70.4770 (2)0.3270 (3)1.3890 (2)0.061 (1)
O80.6715 (5)0.0127 (7)1.4919 (6)0.068 (4)0.59 (1)
O90.658 (3)0.078 (2)1.434 (2)0.095 (15)0.17 (1)
HO4a0.63590.39590.98160.030*
HO4b0.61570.47570.86730.030*
HO8a0.58820.05341.52280.100*0.59
HO8b0.64780.03531.41890.100*0.59
H21.10520.56030.88630.029*
H31.11800.80520.83140.037*
H41.00290.94340.67010.039*
H50.87230.83890.56150.032*
H70.79910.63240.51260.026*
H8a0.78190.33280.47920.030*
H8b0.68110.46450.47920.030*
H9a0.52740.35730.68980.032*
H9b0.55330.24540.60400.032*
H100.55410.04510.76880.028*
H120.58770.19260.89130.033*
H130.66810.35321.06430.035*
H140.79910.27571.19250.033*
H150.85930.03961.14280.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V0.0160 (1)0.0146 (1)0.0156 (1)0.0026 (1)0.0039 (1)0.0034 (1)
O10.0216 (6)0.0150 (5)0.0251 (6)0.0032 (5)0.0094 (5)0.0032 (5)
O20.0250 (6)0.0152 (5)0.0185 (6)0.0047 (5)0.0073 (5)0.0025 (4)
O30.0227 (6)0.0189 (6)0.0223 (6)0.0019 (5)0.0028 (5)0.0062 (5)
O40.0259 (7)0.0255 (6)0.0163 (6)0.0045 (5)0.0018 (5)0.0020 (5)
N10.0172 (7)0.0238 (7)0.0153 (7)0.0029 (6)0.0022 (5)0.0027 (5)
N20.0199 (7)0.0283 (8)0.0147 (7)0.0061 (6)0.0044 (5)0.0035 (6)
C10.0207 (8)0.0155 (7)0.0171 (8)0.0033 (6)0.0011 (6)0.0033 (6)
C20.0296 (9)0.0220 (9)0.0204 (9)0.0067 (7)0.0027 (7)0.0057 (7)
C30.0421 (11)0.0234 (9)0.0246 (9)0.0115 (8)0.0010 (8)0.0106 (7)
C40.0462 (12)0.0166 (8)0.0272 (10)0.0052 (8)0.0039 (9)0.0071 (7)
C50.0342 (10)0.0177 (8)0.0206 (9)0.0014 (7)0.0018 (7)0.0015 (7)
C60.0225 (8)0.0183 (8)0.0170 (8)0.0009 (6)0.0020 (6)0.0036 (6)
C70.0197 (8)0.0232 (8)0.0161 (8)0.0016 (7)0.0003 (6)0.0006 (6)
C80.0245 (9)0.0335 (10)0.0158 (8)0.0074 (8)0.0062 (7)0.0014 (7)
C90.0227 (9)0.0374 (10)0.0192 (9)0.0094 (8)0.0080 (7)0.0013 (7)
C100.0221 (8)0.0302 (9)0.0192 (8)0.0106 (7)0.0032 (7)0.0066 (7)
C110.0197 (8)0.0225 (8)0.0207 (8)0.0063 (7)0.0007 (7)0.0065 (7)
C120.0258 (9)0.0260 (9)0.0305 (10)0.0109 (7)0.0022 (8)0.0094 (8)
C130.0253 (9)0.0181 (8)0.0390 (11)0.0065 (7)0.0007 (8)0.0052 (8)
C140.0215 (9)0.0193 (8)0.0363 (11)0.0006 (7)0.0053 (8)0.0014 (7)
C150.0221 (8)0.0199 (8)0.0281 (9)0.0023 (7)0.0077 (7)0.0026 (7)
C160.0175 (8)0.0155 (7)0.0199 (8)0.0024 (6)0.0004 (6)0.0040 (6)
N30.0204 (7)0.0337 (9)0.0188 (7)0.0017 (6)0.0074 (6)0.0001 (6)
O50.0378 (8)0.0289 (7)0.0211 (7)0.0057 (6)0.0020 (6)0.0028 (6)
O60.0551 (11)0.0285 (8)0.0531 (11)0.0038 (7)0.0257 (9)0.0006 (7)
O70.0485 (11)0.1165 (18)0.0193 (8)0.0293 (11)0.0118 (7)0.0224 (9)
O80.060 (2)0.064 (4)0.067 (3)0.017 (2)0.035 (2)0.029 (3)
O90.140 (18)0.048 (10)0.064 (11)0.012 (10)0.012 (10)0.002 (8)
Geometric parameters (Å, º) top
V—O11.820 (1)C13—C141.391 (3)
V—O21.831 (1)C14—C151.386 (2)
V—O31.594 (1)C15—C161.392 (2)
V—O42.225 (1)N3—O51.265 (2)
V—N12.090 (2)N3—O61.241 (2)
V—N22.076 (2)N3—O71.226 (2)
O1—C11.342 (2)O4—HO4b0.856
O2—C161.346 (2)O4—HO4a0.856
N1—C71.290 (2)C2—H20.950
N1—C81.474 (2)C3—H30.950
N2—C101.288 (2)C4—H40.950
N2—C91.464 (2)C5—H50.950
C1—C21.396 (2)C7—H70.950
C1—C61.402 (3)C8—H8a0.950
C2—C31.389 (3)C8—H8b0.950
C3—C41.386 (3)C9—H9a0.950
C4—C51.380 (3)C9—H9b0.950
C5—C61.411 (2)C10—H100.950
C6—C71.442 (3)C12—H120.950
C8—C91.520 (2)C13—H130.950
C10—C111.438 (3)C14—H140.950
C11—C161.410 (2)C15—H150.950
C11—C121.410 (2)O8—HO8a0.855
C12—C131.371 (3)O8—HO8b0.857
V···Vi8.409 (1)
O1—V—O2107.43 (6)C12—C13—C14119.6 (2)
O1—V—O3100.35 (6)C13—C14—C15121.3 (2)
O1—V—O484.62 (6)C14—C15—C16119.4 (2)
O1—V—N185.43 (6)O2—C16—C15119.6 (2)
O1—V—N2160.09 (6)O2—C16—C11120.3 (2)
O2—V—O399.55 (6)C11—C16—C15120.1 (2)
O2—V—O480.93 (5)O5—N3—O6118.7 (2)
O2—V—N1155.40 (6)O5—N3—O7119.4 (2)
O2—V—N286.46 (6)O6—N3—O7121.9 (2)
O3—V—O4174.55 (6)HO4a—O4—HO4b97.9
O3—V—N198.55 (6)C3—C2—H2120.5
O3—V—N291.02 (6)C1—C2—H2120.5
N1—V—N276.69 (6)C4—C3—H3119.5
O4—V—N179.51 (5)C2—C3—H3119.5
O4—V—N283.58 (6)C5—C4—H4120.0
V—O1—C1133.8 (1)C3—C4—H4120.0
V—O2—C16126.6 (1)C4—C5—H5119.8
V—N1—C7125.6 (1)C6—C5—H5119.8
V—N1—C8113.8 (1)N1—C7—H7117.5
V—N2—C9117.0 (1)C6—C7—H7117.5
V—N2—C10122.3 (1)H8a—C8—H8b109.5
C7—N1—C8120.2 (2)N1—C8—H8a110.5
C9—N2—C10120.5 (2)C9—C8—H8a110.5
O1—C1—C2118.8 (2)N1—C8—H8b110.5
O1—C1—C6120.4 (2)C9—C8—H8b110.5
C2—C1—C6120.7 (2)H9a—C9—H9b109.5
C1—C2—C3119.1 (2)N2—C9—H9a110.3
C2—C3—C4121.1 (2)C8—C9—H9a110.3
C3—C4—C5120.1 (2)N2—C9—H9b110.3
C4—C5—C6120.4 (2)C8—C9—H9b110.3
C1—C6—C5118.7 (2)N2—C10—H10117.7
C1—C6—C7121.9 (2)C11—C10—H10117.7
C5—C6—C7119.3 (2)C13—C12—H12119.6
N1—C7—C6124.9 (2)C11—C12—H12119.6
N1—C8—C9105.5 (1)C12—C13—H13120.2
N2—C9—C8106.1 (1)C14—C13—H13120.2
N2—C10—C11124.7 (2)C15—C14—H14119.4
C12—C11—C16118.8 (2)C13—C14—H14119.4
C10—C11—C16122.2 (2)C14—C15—H15120.3
C10—C11—C12118.8 (2)C16—C15—H15120.3
C11—C12—C13120.8 (2)HO8a—O8—HO8b91.1
Symmetry code: (i) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formula[VO(C16H16N2O2)(H2O)]NO3·0.76H2O
Mr426.97
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)9.482 (1), 9.859 (1), 10.324 (2)
α, β, γ (°)74.995 (2), 74.022 (2), 85.559 (3)
V3)896.1 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.60
Crystal size (mm)0.50 × 0.40 × 0.24
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionIntegration
(XPREP; Siemens, 1995)
Tmin, Tmax0.741, 0.872
No. of measured, independent and
observed [I > 3σ(I)] reflections
12081, 4646, 4190
Rint0.074
(sin θ/λ)max1)0.697
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.040, 0.97
No. of reflections4190
No. of parameters264
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.40 (8), 0.81 (8)

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SIR97 (Altomare et al., 1997 ) and KRYSTAL, modified ORFLS (Busing et al., 1962) and KRYSTAL (Hazell, 1995), ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL, KRYSTAL.

Selected bond lengths (Å) top
V—O11.820 (1)V—O42.225 (1)
V—O21.831 (1)V—N12.090 (2)
V—O31.594 (1)V—N22.076 (2)
 

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